Magenta coupler-containing silver halide photographic materials

ABSTRACT

Silver halide photographic materials containing at least one 3anilino-2-pyrazol-5-one type non-diffusing magenta coupler, the phenyl group of the coupler being substituted, in at least one ortho-position thereof, with a halogen atom or an alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, amino, amido, hydroxyl, cyano or nitro group, and in at least one of the meta- and the para-positions thereof, with a sulfamoyl group. The photographic materials containing the magenta coupler(s) are suitably prepared according to an oil solution system. A sharp color image can be reproduced from the photographic material according to a color subtractive process.

United States Patent 1 Arai et al.

[ Sept. 23, 1975 I MAGENTA COUPLER-CONTAINING SILVER HALIDE PHOTOGR APIIIC MATERIALS [75] Inventors: Atsuaki Arai; Yasushi Oishi; Akio Okumura; Minoru Yamada; Yukio Yokota; Kozo Inouye, all of Minami-Ashigara, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

MinambAshigara, Japan [22] Filed: Nov. 13, 1973 [21] Appl. No.: 415,864

[30] Foreign Application Priority Data Nov. 15,1972 Japan 47-114445 [52] US. Cl. 96/100; 96/56; 96/565 [51] Int. Cl. 603C I/40 [58] Field of Search 96/100, 56.5

[56] References Cited UNITED STATES PATENTS 2,343,703 3/1944 Porter et al 96/100 3,127,269 3/1964 Greenhalgh et al. 96/100 3,623,871 11/1971 Poucke et al. 96/100 FOREIGN PATENTS OR APPLICATIONS 670,949 4/1966 Belgium 96/100 Primary Examiner-.I. Travis Brown Attorney, Agent, or FirmSughrue, Rothwell, Mion, Zinn 81. Macpeak 17 Claims, No Drawings MAGENTA COUPLER-CONTAINING SILVER HALIDE PHOTOGRAPHIC MATERIALS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to silver halide photographic materials containing at least one novel magenta coupler.

2. Description of the Prior Art It is known that exposure of silver halide color photographic materials followed by color development thereof causes the formation of indophenols, indoanilines, indamines, azomethines, phenoxazines, phenazines and like dyes due to the reaction of the oxidation products of primary aromatic amine developing agents and the couplers, resulting in the formation of color images. In this type a subtractive process for color reproduction is generally used, and yellow, magenta and cyan color images, which are complementary colors of blue, green and red, respectively, are formed. In general, acylacetamide or dibenzoylmethane type couplers are used for the formation of yellow images; pyrazolone, cyanoacetyl or indazolone type couplers are used for the formation of magenta images; and phenol type couplers such as phenols and naphthols are used for the formation of cyan images.

In these color photographs, the couplers for forming the dyes are either added in the developers employed or incorporated in photo-sensitive emulsion layers. Thus, the reaction of the oxidation products of the color developing agents formed in thedev'elopment of latent images with couplers happens during development.

Various kinds of 2-pyrazol-5-one derivatives for forming magenta images are known. For example, an alkoxy group (as described in US. Pat. No. 2,439,098), an aeylamino group (as described in US. Pat. Nos. 2,369,489 and 2,600,788) and a ureido group (as described in US. Pat. No. 3,558,319), and an alkyl group, an aryl group and :an anilino group are known as substituents in the 3-position of the S-pyrazolone ring of these derivatives. 3-Anilino-5-pyrazolone type couplers have often been described since the issuance of US. Pat. No. 2,311,081 (Re. 22329), and some improvements thereon have been proposed. In this connection, British Patent No. 956,261 discloses that azomethine dyes obtained from such derivatives having an .alkoxy or halogen substituent in the ortho-position to theanilino group have advantageous spcctroabsorption for such color photographs, having an especially narrow absorption of undesired range of red light. Nondiffusing couplers belonging to this type and which-can be incorporated into photographic emulsions are the known 3-(acylamino-anilino)-2-pyrazol-5-ones of the following formula:

D CONH wherein D represents an aryl group, D CO represents an acyl group. D; represents hydrogen atom or a coupling off group removed by the oxidation product of a primary aromatic amine developing agent, such as phenoxy group. and L represents a chlorine atom or a methoxy group.

When these couplers are used by addition previously to silver halide photographic emulsions during the preparing of the photographic materials (incorporated couplers), these couplers must be non-diffusing cou plers in order to prevent such an unfavorable phenomenon in which the incorporated couplers diffuse between emulsion layers of different spectral sensitivities and mutually admix together consequently decreasing the color reproducibility thereof. For this reason, it is necessary to introduce into the coupler molecule a hydrophobic group having 8 or more carbon atoms as a ballast group, which serves to decrease the diffusibility of the coupler.

The following methods, which can be classified into roughly three groups, have been previously used for the incorporation of non-diffusing couplers into photographic emulsion layers:

1. Water solution system: Couplers having watersoluble groups such as a carboxyl group or a sulfonic acid group are soluble in alkaline aqueous media, and after the coupler is added to an emulsion in the form of a neutral or alkaline aqueous solution, this is neutralized with an acid. I

2. Oil solution system: A coupler is dissolved in an organic solvent and the resulting organic solution containing the coupler is emulsified and dispersed in an aqueous medium inthe form of fine colloidal particles, and then the resulting dispersion is added to av photographic emulsion.

3. A coupler is heated and melted, and the molten coupler is directly added to an emulsion or an aqueous medium to disperse the same.

In order to form green-sensitive photographiccmulsion layers having excellent properties by using magenta couplers suitable for the oil solution system,1the following characteristics are required: (1 the couplers should have high coupling reactivity with the oxidation products of developing agents; 2) the magenta color images formed through color development should have suitable light absorption characteristics in accordance with the color reproduction principles of the trichromatic subtractive process; (3) the magenta color images should not deteriorate but, should be fast even when stored under any severe conditions; (4) the couplers shouldnot adversely affect photographic emulsions; and (5) the couplers should be easily soluble in organic solvents for dispersing the couplers, and further should be difficult to crystallize in organic solvents.

Magenta couplers for the oil solution system which have heretofore been known do not have sufficient coupling reactivity with the oxidation products of developing agents in the form of a dispersion in an emulsion layer, and thus, it has been difficult using the oil solution system to obtain greensensitive emulsion layers having excellent photographic properties.

A magenta color image in trichromatic subtractive color photography absorbs light in the range of wavelength of maximum luminosity, and therefore, the light absorption characteristic thereof is an extremely important factor for determining the properties of color photographs for color reproduction. In particular, it has been believed that improvement in sharpness of the spectroabsorption curve and a decrease of specific secondary absorption of the pyrazolone type magenta couplers will result in good absorption characteristics of the magenta color image in question, and various efforts have been directed toward attaining such advantages,

Magenta color images obtained from conventional magenta couplers tend to be deteriorated when stored under conditions of high temperature and high moisture for a long period of time, and the use of formalin has been inevitable during development treatment for preventing this deterioration.

SUMMARY OF THE INVENTION A fourth object of this invention is to provide photographic materials suitable for simple development treatment which do not require any stabilization treatment with formaldehyde or the like.

A fifth object of this invention is to manufacture photographic materials by using magenta couplers which may be synthesized relatively easily from easily available materials.

These and other objects of this invention can be attained in accordance with the invention as set forth in detail in the description and Examples to follow.

The objects of this invention can be attained by incorporating at least one 3-anilino-2-pyrazol-5-one derivative as a magenta coupler into at least one silver halide emulsion layer of a photographic material, in which the anilino group of the derivative is substituted in at least one ortho-position thereof, with a halogen atom or an alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, amino, amido, hydroxyl, cyano or nitro group, and in at leastone of metaand para-positions thereof, with a sulfamoyl group. The 4-position of the 2- pyrazol-S-one derivative can be substituted by a residue which may be removed by means of an oxidation product ofa primary aromatic amine developing agent.

DETAILED DESCRIPTION OF THE INVENTION Especially preferred couplers of this invention include compounds of the following general formula (I):

- nyl,

wherein R represents an aryl group in which the aryl groups include any of the substituted groups used in couplers, such as a halogen atom, a cyano group, a nitro group, a hydroxy group. a earboxy group, an amino group (e.g.. amino, N-alkylamino, N,N- dialkylamino, N-arylamino, N-alkyl-N-aryl-amino. etc.), a earboxy ester (e.g., carbomethoxy, carboethoxy, carbophenoxy. etc.), a sulfo group, a sulfo ester (e.g., methoxysulfonyl, butoxysulfonylphenoxysulfonyl, etc.) an amido group (e.g., acetamido, butyramido, [a-(2,4-di-t-amylphenoxy)acetamido1benzamido. oz- (3 pentadecylphenoxy )butyramido, a-( 4-tbutylphenoxy)propionamide, 3,5- dicarboxybenzamido, ethylsulfonamido, phenylsulfoamido, etc.), a carbamyl group -(c.g.. N- methylcarbamyl, N-phenylcarbamyl, etc.), a sulfonyl group (eg. N-propylsulfamyl, N-tolylsulfamyl, etc.), an alkoxy group (e.g., methoxy, butoxy, etc.), an aryloxy group (e.g., phenoxy, tolyloxy, naphthoxy, etc.), (for example, phenyl, Z-chlorophenyl, 4-chlorophenyl, 2,5-diehlorophenyl, 2,6-dichlorophenyl, 2,4,6- trichlorophenyl, 2-bromophenyl, 3,5-dibromophenyl, 2-cyanophenyl, 4-cyanophenyl, 3-nitrophenyl, 4- nitrophenyl, 4-tolyl, 2,6-dimethylphenyl, 2,6- diethylphenyl, 4-butylphenyl, Z-trifluoromethylphenyl, 2-ethoxyphenyl, 4-phenylphenyl, 4-phenoxyphenyl, N- methylbenzamidophenyl, N,N-diphenylcarbamylphe- N,N-diphenylsulfamylphenyl, N,N-dibutylsulfamylphenyl, phenyl-N-methyl-sulfonamido-phenyl, Z-methyI-S-nitrophenyl, 2-chloro-5 -cyanophenyl, 5-chloro-2-methylphenyl, 2,6-dichloro-4- methylphenyl, 2,4-dichloro-6-methylphenyl, 2-chloro-4,6dimethylphenyl, 2,6-dichloro-4 methoxyphenyl, 2,6-dichloro-4-nitrophenyl, 2,4,6- trimethyl-3-nitrophenyl, 2,4,6-trimethyl-3-substituted aminophenyl, 2,6-dichloro-4-methoxycarbonylphenyl, 2,6-dichloro-4-benzyloxycarbonylphenyl, or 2,6-dichloro-4-carboxyphenyl group, etc.) or a heterocylic group (for example, a residue ofa five or six membered heterocyclic compound such as Z-thiazolyl, 2- benzothiazolyl, 2-benzoxazolyl, 2-oxazolyl, 2- imidazolyl, or 2-benzimidazolyl group;

R and R each represents a hydrogen atom, a straight or branched alkyl group having I to 32 carbon atoms, a cycloalkyl group (for example, a cyclohexyl group, terpenyl group, norbornyl group, etc.), an aryl group (for example, a phenyl group, a naphthyl group, etc.) or a heterocyclic group (for example, a benzimidazolyl group, a benzothiazolyl group, etc.), or represents a group of non-metal atoms necessary for forming, together with the N-atom of tthe sulfamoyl group, a heterocyclic ring such as morpholine or piperidine; the alkyl, aryl and heterocyclic groups, etc. can optionally be substituted with at least one substituent such as a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, an amino group (for example, an unsubstituted amino group, an alkylamino group. a dialkylamino group. an anilino group, an N-alkylanilino group, etc.) an aryl group, a carboxy ester group (for example, a earboalkoxy group, a carboaryloxy group, etc.), an amido group (for example, an acetamido group, a butylamido group, an ethylsulfonamido group, an N- mcthylbenzamido group, an N-propylbenzamido group, a 4-tert-butylbenzamido group, a diaeylamido group, etc. a earbamyl group (for example, an unsubstituted carbarnyl group, an N-octadecylcarbamyl group, an N,Ndihexylcarbamyl group, an N-methyl-N-phenyl-carbamyl group, a 3pentadecylphenylcarbamyl group, etc.) a sulfamyl group (for example. an N-propylsulfamyl group, an N-tolylsulfamyl group, etc.) an alkoxy group (for example, an cthoxy group, an octadecyloxy group, etc), an aryloxy group (for example, a phenoxy group, a tolyloxy group, a naphthyloxy group, etc.), a sulfonic acid group, a sulfonyl group (for example, a methylsulfonyl group, an octadecylsulfonyl group, an ethoxysulfonyl group, a decyloxysulfonyl group, a phenylsulfonyl group, a tolysulfonyl group, a phenoxysulfonyl group, etc.) or the like; X and Y each represents an alkyl group (for example, a methyl group,a tert-butyl group, an octyl group, a dodecyl group, etc. an aryl group (for example, a phenyl group, a tolyl group, etc.) an alkoxy group (for example, a methoxy group, an octyloxy group, etc.), an aryloxy group (for example, a phenoxy group, a p-tertbutylphenoxy group, a naphthoxy group, etc.), an alkylthio group (for example, a methylthio group, an octylthio group, etc), an arylthio group (for example, a phenylthio group, etc.), an amino group (for example, an unsubstituted amino group, a methylamino group, a diethylamino group, an anilino group, etc.), an amido group (for example, an acetamido group, a butylamido group, a methylsulfonamido group, a diacylamido group, etc.) a halogen atom (for example, fluorine, chlorine, bromine, etc.), a hydroxyl group, a cyano group or a nitro group, and Y can be a hydrogen atom; Z represents a hydrogen atom or a residue which can be removed by coupling, such as a thiocyano group, an acyloxy group (for example, an aeetoxy, dodecanoyloxy, octadecanoyloxy, 3-npentadeeylphenoxyacetoxy. benzoyloxy, betanaphthoyloxy, 3-! 4-( 2,4-di-tert-pentylphenoxy butylamidolbcnzoyloxy or the like group), an aryloxy group (for example, a phenoxy, p-chlorophcnoxy, pnitrophenoxy, naphthoxy or the like group), a halogen atom (for example, chlorine, fluorine, etc.), an arylazo group (for example, a substituted or an unsubstituted phenylazo or naphthylazo group, etc. a Z-aryltriazolyl group (for example, a Z-benzotriazolyl, 2- naphthotriazolyl or the like group), an alkylthio group (for example. containing an alkyl group of 4 to 1() carbon atoms), an arylthio group (for example, a phenylthio, naphthylthio or the like group). a heterothio group (for example. a 2.-benzothiazolythio, l-phenyl-S- tetrazolylthio, Z-benzoxazolylthio, 2- benzimidazolythio. 5-phenyl-l,3, 4-oxadiazolyl-2-thio or the like group). a cycloalkylthio group (for example, a cyclohexylthio group. etc), a eycloalkoxy group (for example. a cyclohexyloxy group, etc.) or the like.

An especially preferred embodiment of R is represented by the following formula:

2 S in which U, represents a halogen atom. an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an

aryloxy group, an arylthio group or a cyano group; U

represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or a cyano group; and U U and U each represents a hydrogen atom, a halogenatom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, arylthio group, a cyano group, an acylamino group, a earbamyl group, an ureido group, a sulfonamido group, a sulfamyl group, an alkylsulfonyl group, a alkylcarbonyl group, an alkoxycarbonyl group, an aralkoxycarbonyl group, a carboxy group or an arylcarbonyl group.

The magenta coupler molecule represented by the above formula (1) preferably contains therein at least one hydrophobic group having 8 to 32 atoms as a ballast group. The hydrophobic group makes the coupler easily soluble in an organic solvent making the coupler solution easily dispersible in a hydrophilic colloid, as well as preventing the coupler from being crystallized thereby stabilizing the resulting photographic material. If the number of carbon atoms of the hydrophobic group is less than 8, the coupler will dissolve in a treating solution such as developer and will move in the photographic material consequently decreasing the color reproducibility thereof, while, on the contrary, if the number of carbon atoms is more than 32, the mutual interaction between coupler molecules becomes too great and the couplers become difficultly soluble in organic solvents. Usse of couplers containing ballast groups outside of the range of 8 to b 32 carbon atoms is disadvantageous. Representative examples of such hydrophobic ballast groups are, for example, an alkyl group, an alkoxyalkyl group, an alkenyl group, an aryl group substituted with alkyl group(s), an aryl group substituted with alkoxy group(s), a terphenyl group, etc. These hydrophobic groups can be substituted with, for example, a halogen atom such as a fluorine atom or a chlorine atom, or a nitro group, a cyano group, an alkoxycarbonyl group, an amido group, a earbamyl group, a sulfonamido group, etc. Specific examples of such hydrophobic groups are, for example, n-octyl, 2- ethylhexyl, tert-octyl, n-nonyl, n-decyl, n-dodecyl, 1,1- dimethyldeeyl, 2,2-dimethyldecyl, n-octadeeyl, 2-(nhexyl)-decyl, n-oetadecyl, 9,10-dichlorooctadecyl, heptyloxyethyl, 2,4-di-tert-pentylcyclohexyldodecyloxypropyl, oleyl. 2,4-di-tert-butylphenyl, 2,4-di-tertpentylphenyl, 2,4-di-tert-pentyl-6-chlorophenyl, 3-npentadecylphenyl, 2-dodecyloxyphenyl, 3- heptadecyloxyphenyl, O-terphenyl or perfluoroheptyl groups.

These hydrophobic residues are included in at least one of the groups represented by R, R R X, Y and Z in the above formula (I). These hydrophobic residues can constitute the R. R R X, Y and Z groups, by themselves or in combination with other aliphatic or aromatic groups or hcterocyclic groups bonded with the hydrophobic residues directly or via a divalent bond such as an ether bond, a thioether bond, an amide least one ortho-position thereof an alkyl, alkoxy or I alylthio group or a halogen atom or acyano group as a substituent having excellent heat and light stability, those in which one or both of R and R are unsubstitued alkyl groups or alkyl groups substituted with an alkoxy, aryloxy, acyloxy, alkoxycarbonyl, acylamino,

atoms included in these groups R, and R is in the range of 8 to 32 are advantageously synthesized, those in which X is a halogen atom, an alkoxy group having or less carbon atoms or an aryloxy group having '12 or less carbon atoms are advantageous in that the spectroabsorption characteristics of magenta images formed therefrom are excellent, those in which Y is a hydrogen atom have the advantage that the raw materials forsynthesis of the couplers are readily available and that the synthesis thereof is advantageous, and those in which the R R NsO -moiety in the anilino I group is in the 5-position are excellent in that they are easily soluble in solvents for couplers. I The magenta couplers used in the present invention also include derivatives of S-pyrazolotie compounds of the formulatl), such as 3-anilino-5-acyloxypyrazoles obtained by reacting the S-pyrazolone compounds, with acylating agents, and the alkylidene-bispyrazolones and arylidene-bis-pyraiolones obtained by reacting the S-pyrazolorie compounds with aldehydes. Representative examples of magenta couplers which can be used in the present invention are described below, the listing of which, however, should not be interpreted as limiting the scope of the present inventionl-(2,4,6-Trichlorophenyl)-2-pyrazol 5 one 'cornpounds having the following 3-substituent:

l. 3-'[ 2-chloro-4-( tetradecyl-sulfamoyl)anilino]- substituent,

2. 3-[2-chloro-5-(tetradecylsulfamoyl)anilino]- substituent, v

3. 3-[2-chloro-5-(dodecylsulfamoyl)anilino]- substituent,

4. 3-[ 2-ch loro-5 1,1-dimethylhexadecylsulfamoyl- 3-[5-diethylsulfamoyl-2- carbamyl or like group, and the total number of carbon l2. hydroxyphenoxy)tetradecylsulfa moyl]anilino}- substituen't' i l3. 3 2{methyflthio-S-hexadecylsulfamoyl)anilinolsubstituent, i i l4. 3-[2-chloro-5- (tetradecylsulfamoyl)anilino]-4- "(4-methoxyphenylazo )-substituent, and

15. 3-[Z-ChIoro-S-tdodecylsulfam'oyl)anilino]-4 (4- chlorophenoxy )-s'ubstituent. 1'- (2 chloro 4,6-dimethylphenyl)-2-pyrazol-5-one compounds having the'following 3-substituentz 16. 3-[2-chlor o- 5-(dodecylsulfamoyl)anilino]- I substituent, f l7. 3-[2-chloro-5-(N-2-cyanoethyl-N- hexadecylsulfamoyl)anilino]-substituent,

, penthylphenoxy)propylsulfamoyl]-anilino} substituent, i

19. 3-.{2,5-dichloro-4-[ 3 (2,4-di-tert-pentylphenoxy) propylsulfamoyl]anilino} -substituent, and

20. 3- {2 met hoxy-5-[ 3-(2,4-di-tert-pentylphenoxy) v propylsulfamoyH-anilino}-substituent. ..l-(2,6-dichloro-4-methoxyphenyl )-2-pyrazol-5-one compounds having the. following 3-substituent or the following derivative thereof: 7 i

v 21 3-[Z-rnethoxy-S-(tetradecylsulfamoyl)anilino]- substituent,

. 22. 3-[;2 -chloro-5-(N-methyl N-octadecylsulfamoyl) anilino]-substituent,

23. 3- (2-chloro-.5- [3-(2,4-di-tert-pentylphenoxy) propylsulfamoyl]-anilino}-substituent, 24. 3-{2-chloro-5-[4-(2,4-di-tertpentylphenoxy) bu- 1 tylsulfamoyl]-anilino.}-substituent, I

1 pentadecylphenoxy)propylsulfamoyll-anilino}-- substituent, f r

26.. 3-[,2-chlor0-5-(4-dodecylphenylsulfamoyl) anilino]-4-( l-naphthylazo )-derivative,

27. -3-{2-methoxy-5-[3-(2,4-di-tert-pentylphenoxy) propylsulfamoyl]-anilino}-4-(3,5-dimethyl-4- pyrazolylazo)-derivative, and 1 28. 3- {2-chloro-5-[4-(2,4-di-tert-pentylphenoxy) butylsulfamoyl ]-anilino}-4=acetoxy-derivative.

Other derivatives of Z-pyrazol-S-one compounds as follows: r

'29. l-( 2,5-dichlorophenyl)-3-[ 2-chloro-4-(N- 'methyl-N-octadecylsulfamoyl)anilino]-derivative, 30.= '1-(4,6-dichloro-2methylphenyl)-3-(5- dodecylsulfamoyl-2-methylamilino)-derivative, 31. l-(2,6-dichloro-4-methylphenyl)-3-(4- dodecylsulfamoyl-2emethoxyanilino)-derivative,

32. l-(4-chlorophenyl)-3- {2-chloro-5-[2-(N- butylhexadecylamido)-ethylsufamoyl]anilino} -derivative, 1

3'3. 1-(4-sulfophenyl)-3-[2-chloro-5-(tetradecylsulfamoyl)anilinobderivative,

pentylphenoxyacetamido)phenyl]-3(5- diethylsulfamoyl-Z-methoxyanilino)-4-( l-phenyl- S-tetrazolythio)-derivative,

35. I l [2,4,6-trimethyl-3-( 2,4-di-tertpentylphenoxyacetamido)-phenyl]-3-[2-chloro-5- (morpholinosulfonyl) anilino]-derivative,

" 'rolidinylsulfonyl anilinol-derivative,

l-2,6-dichloro-4-(2,4-di-tert-i 37. l-{2.6-dichloro-4-[4-( 2,4-di-tertpcntylphenoxy )butylamidol-phenyl}-3-(4- diethylsulfamoyl-Z-methoxyanilino)-derivative, and

pentylphenoxy)butylamido]-phenyl}-3-[2,5- dichloro-4-cyc1ohexylsulfamoyl)anilino1- derivative,

39. l-(2,6-dichloro-4-methoxycarbonylphenyl)-3-[2- chloro-4-(tetradecylsulfamoyl)anilinoJ-derivativc,

40. 1-(2,6-dichloro-4-methoxycarbonylphenyl)-3-[2- chloro-5-(hex'adecylsulfamoyKanilino]-derivative,

41. l-(2-chloro-3,5-dimethoxycarbonylphenyl)-3-[2- methoxy-5(tetradecylsulfamoyl)anilino]- derivative,

42. 1-(2-chloro-5-methoxycarbonylphenyl )-3-[2- chloro-4-(N-methyl-N-octadecylsulfamoyl- )anilino]-derivative,

43. 1-( 2,6-dichloro-4-ethoxycarbonylphenyl )-3-{2- chloro-5-[3-(2,4-di-tert-pentylphenoxy)propylsulfamoyl]-anilino} -derivative,

44. l-(2,6-dichloro-4-methoxycarbonylphenyl)-3-[2- chloro-S-(dodecylsulfamoyl)anilino]-4-(2- naphthylazo)-derivative.

The magenta couplers which are used in the present invention can be prepared using conventional methods. Some examples to show the synthesis of representative couplers will be given below. Other couplers according to the present invention can also be prepared in a similar manner.

SYNTHESIS EXAMPLE 1 1-( 2,4.6-Trichlorophenyl )3- {2-chloro-5- dodecylsulfamoyl)anilino}-2-pyrazol-5-one [Coupler )1 100 g of 2-chloro-5-dodecylsulfamoyl-aniline were dissolved in 500 ml of chloroform. The resulting solution was added dropwise into a dispersion of 60 g of thiophosgene in 500 ml of waterat l-15C while stirring. After stirring for hours, the chloroform layer was separated and washed with water, and then chloroform was distilled off under reduced pressure. The residue was recrystallized from ligroin to obtain 2-chloro- 5-dodecylsulfamoylisothiocyanate, the melting point of which was 6770C.

After 2.3 g of sodium metal were dissolved in 150 ml 'of methanol, 13g of ethyl acetoacetate were added thereto. To the resulting solution were added 40 01'2- chloro-S-dodecylsulfamoylisothiocyanate, and the entire amount was heated for minutes under reflux. After cooling, 16g of methyl iodide were added thereto, and the reaction mixture was again heated for 30 minutes under reflux. After distilling off the excess methyl iodide, 28g of 2,4,6-trichloro-phenyl hydrazine lwere added and the mixture heated for.16 hours under reflux. The methanol was then distilled off under re- *duced pressure and the residue was dissolved in 150 ml of acetic acid. The resulting acetic acid solution was poured into water, and the resinous product formed therefrom was collected and recrystallized from acetonitrile to obtain the above Coupler (3). The melting point thereof was 138-14lC.

1-{2,4,6 trimethyl-3-[2-(2,4-di-tert- 5 1-('2,4,6-trichlorophenyl )-3amino-2- 19.2g of 2-chloro-5-3-(2,4-di-tertpentylphenoxy)propylsulfamoyl aniline and 78.4g of phosphoric acid were stirred for 2 hours in a nitrogen gas atmosphere while heating the reaction mixture to keep the temperature at 170190C. The reaction mixture was extracted with hot acetonitrile and the extract cooled with ice, whereby asmall amount of colored by-product immediately separated out. The separated by-product was filtered off and the filtrate was left to stand as such, whereby the desired product was obtained. The product was recrystallized from acetonitrile to form colorless crystals having a melting point of 173-175C.

SYNTHESIS EXAMPLE 3 l-(2,6-Dichloro-4-methoxyphenyl )-3-[ 2-chloro-5-{ 3- (2,4-di-tert-pentylphenoxy )propylsulfamoyl} anilino]- 2-pyrazol-5-one [Coupler (23)] 20.0g of ethyl-3-ethoxy-3-ethylmercapt0-acrylate synthesized according to a method of G. Barnikow, et at. [Chem Ber., 100, 1428 (1967)] and 48.0 g of 2- chloro-S-{3-(2,4-di-tert-penthylphenoxy)propylsulfamoyl aniline were heated for 2 hours at 150170C and stirred. Without isolating and purifying the ethyl-3- [2-chloro-5- {3-( 2,4-di-tertpentylphenoxy )propylsulfamoyl} -anilino]-3-ethoxyacrylate obtained, 18.0 g of 2,6-dichloro-4- rriethoxyphenyl hydrazine and 90 ml of acetic acid were added thereto and the mixture was heated for 2 hours under reflux. Acetic acid was distilled off from the reaction mixture, and after 100 ml of acetonitrile were added thereto and the mixture left to stand as such, the desired product was collected. The colorless crystals obtained after recrystallization of the said product from a mixed solvent of acetonitrile and ethanol had a melting point of 17ll74C.

SYNTHESIS EXAMPLE 4 1-( 2,4,6-Trichlorophenyl )3-{2ch1or0-4- (tetradecylsulfamoyl )-anilino} -2-pyrazol-5-one [Coupler (1)] 19.0 g of ethyl-3,3-diethoxy-acrylate synthesized according to a method of SA. Glickman, et at. [.I. Am.

'Chem. Soc., 67, 1017 (1945)]and 39.0 g of 2-chloro-4- tetradecylsulfamoylaniline were heated and stirred for 5 hours at l501 C. Without isolating and purifying the ethyl3-[2-chloro-4-tetradecylsulfamoylanilino]-3- ethoxyacrylate obtained, 16.0 g of 2,4,6- trichlorophenyl hydrazine and 100 ml of acetic acid were added thereto, and the mixture was heated for 2 hours under reflux. After acetic acid was distilled off from the reaction mixture and ml of acetonitrile were added thereto and the mixture left to stand as such, the separated product Coupler l was collected. The colorless crystals obtained after recrystallization of the said product from a mixed solvent of ethanol and acetonitrile had a melting point of 176 179C.

The magenta couplers according to the present invention have high coupling reactivity and sufficient solubility in organic solvents, and thus, photographic materials for color photography prepared using these couon the anilino group. The couplers of the present inventhe form of an ethyl acetate solution thereof. The dyes plers have excellent photographic properties such as good sensitivity, gradation, etc. and further. these materials are advantageous'in that they can easily be prepared. In addition'JphOtOgr'aphic color images obtained after development of the materials have'advantageous spectroabsorption characteristics and sufficient fastness in color reproduction, and they are stable on storage for a long period of time under severe conditions. The characteristic features of the present invention will hereinafter be described in detail.

The 3-anilino-2-pyrazol-5-one type couplers of the formula (I) which are used in the present invention are structurally different from known couplers as disclosed in British Patent No. 956,261 and US. Pat. No. 3,419,391 and Japanese Patent Publn. No. 19032/71, in that the couplers of the formula (I) of the invention contain a sulfamoyl group on the anilino group thereof while the known couplers contain an acylamino group tion which have a sulfamoylanilino group yield color images of more excellent spectroabsorption characteristics than the other known couplers having an acylaminoanilino group. This is because the couplers of the present invention form azomethine dyes having less undesirable absorption of red light and blue light, and thus, photographic materials for color photography can be prepared using the advantageous couplers of the present invention which can reproduce light and sharp red color and blue color. In addition, the 2-pyrazol- S-one type couplers which have a sulfamoylanilino group and which areused in the present invention can more easily be made soluble, in general, in organic s01- vents than the other couplers containing an acylamino group and corresponding to those of the present invention.

Comparing the couplers used in the present invention with the 3-acylaminoand the 3-ureido-2-pyrazol- 5 one couplers which have heretofore been known as magenta couplers with the most excellent properties, it is noted that the couplers of the present invention are improved in that they yield images of more excellent spectroabsorption characteristics, that they have higher reactivity with the oxidation products of primary aromatic amine developing agents, that the color images obtained have more excellent heat durability, and that no specific aftertreatment is necessary for stabilizing the color images obtained due to the high heat durability thereof. These improvements attained in the present invention will bespecifically substantiated by experimental data to follow.

i. Spectroabsorption characteristics of dyes:

The spectroabsorption characteristics of the azomethine dyes which form color images were compared in 12 1-(2,4.6-Trichlorophenyl)-3-{2-chloro-4-[4-(2,4-ditert-pentylphenoxy)-butylamindo]ani1ino}-2- pyrazol-S-one Known Coupler (B) having 3-acylamino group: 1-(2.4,6-Trichlorophenyl)-3-{3-[2-(2,4-di-tertpentylphenoxy)acetamido]-benzamido}-2- pyrazol-S-one A spectroabsorption curve of each dye was obtained under those conditions in which the density in the maximum absorption wavelength (first absorption) was made 1.0. From this spectroabsorption curve were obtained a second absorption density (1) in a range of a blue light, a density (11) at'a longer wavelength by 60 my. from the first absorption wavelength, and a width of wavelength (111) having a density of 0.5, and these data are shown in the following Table 1.

TABLE 1 ABSORPTION CHARACTERlSTlCS OF DYES FORMED Coupler (l) ("l (111) Invention Coupler l) 0.1 18 0.1 17 64 Invention Coupler (2) 0.128 0.120 64 Known Coupler (A) 0.147 0.165 Known Coupler (B) 0.231 0,237 82 whole with a decrease in the amount of non-volatile organic solvents of high boiling points incorporated in emulsions, as compared with the color images formed using a large amount of non-volatile organic solvents of high boiling points, and therefore, the ability to reduce the amount of solvents for these known couplers is limited from the standpoint of spectroabsorption characteristics. On the contrary, the variation of spectroabsorption wavelength of images from the 3-anilino-2- pyrazol-S-one couplers of thepresent invention is very slight even after a decrease in the amount of solvents used for couplers, and thus, very little limitation in this respect exists. Therefore, the couplers of the present invention are extremely advantageous in that the thickness of emulsion layers can be thin. e.g., 1 to 8 u, more preferably 3 to 6 1.,

ii. Solubility of couplers in organic solvents:

With respect to the use of oil-soluble couplers, it is advantageous to first dissolve the couplers in organic solvents, then to disperse the solution in aqueous media, and thereafter to add the dispersion to photo-.

graphic emulsions. For this, it is preferred that the couplers have a high solubility in the organic solvents. The Couplers (l). (3), (6) and (23) of the present invention were compared with the following known Couplers (A), (C), (D) and (E) which have an acylaminoanilino group, with respect to the solubility thereof in ethyl acetate at 25C, and the results obtained are shown in the following Table 2. 7

Known Coupler (A): above described Known Coupler (C): l(2.4.6-Trichlorophenyl)-3-{2- methoxy-4-[2-(2.4-di-tert-pentylphenoxy)- butylamido]anilino}-2-pyrazol-5-one Known Coupler (D): l-(2.4,6-Trichlorophenyl)-3- {2-chloro-5-[2-(2.4-di-tertpentylphenoxy)- butylamido]anilino}-2-pyrazol-5-one Known Coupler (E): l-(2,4,6-Trichlorophenyl)-3- {2-chloro-5-[ 4-( 2,4-di-tertpentylphenoxy butylamino]anilino}-2-pyrazol-5-one Dialkylphenoxy-alkylcarbonyl groups which are most generally used as a ballast residue of oil-soluble couplers were selected as the acyl group of these known couplers.

TABLE 2 SOLUBILITY OF COUPLERS IN ETHYL ACETATE As can be seen from the results set forth in Table 2. 2-pyrazol-5-one type couplers containing a 3- sulfamoylanilino group which are used in the present invention have lower melting points and higher solubility, as compared with known couplers containing a 3- acylaminoanilino group. The Couplers (6) and (23) of the present invention show a heat of solution of 3.30 k cal/mole and 3.48 k cal/mol, respectively when dissolved in a large amount of ethyl acetate at 25C. These heats of solution and the relatively low melting points of these Couplers mean that these Couplers have sufficient solubility to attain the objects of the present invention even at a low temperature. As a result, the couplers which are used in the present invention are easily dispersible and the amount of coupler solvents necessary for dissolving the couplers can be small. and theregfore, when non-volatile coupler solvents are used. the

amount of solvent remaining in the coated emulsion 'films is consequently small. Accordingly. the thickness of the coated emulsion films can be reduced, whereby scattering of light in the thinner emulsion films decreases with the result that sharp images can be methanesulfonamidoethyl)amino}- 2-methylaniline in i the presence of a cyan forming coupler T22-[2- (2.4-di-tertpentylphenoxy)-acetamido]-4,6-dichloro- 5-methylphenol. and the relative coupling speed was calculated therefrom in each case. The relative coupling speed is calculated as follows: The coupling reactivity ofa coupler is determined relatively by measuring each content of dyes in color images which are obtained by adding two kinds of Couplers M and N. which yield mutually clearly separated different dycs. to an emulsion in the form of a mixture ofthese two couplers and then subjecting the resulting photographic material to color development. When the Coupler M yields an image having a maximum density of (D and a midway density of D and the Coupler N an image having (D and Dy, respectively. the ratio of the reactivities of the both couplers R /R is represented by the following formula:

I {I R..- log 1K)...

h results of log IIIIIJ of a plurality of the couple of D and D which are obtained from color images formed by subjecting an emulsion containing the mixed couplers to to several stages of exposure followed by color development are plotted on a vertical-horizontal biaxial graph to determine a line. from the slope of which is calculated-the above coupling reactivity ratio R /R The relative coupling speed thus obtained in each It can be seen from the results set forth in the above Table 3 that the Couplers (l and (6) of the present invention react with the oxidation product of the color developing agent used at a higherspeed than the other known Couplers (A) and (B). As a result. color photographic materials of the present invention have greensensitivity, high magenta density and good gradation, and further can form excellent color images.

(iv) Stability of color images:

The magenta color images obtained from the new couplers of the present invention have various favorable characteristics such that they are fast to the action of heat and moisture and that they are hardly deteriorated even after exposure to strong light. It is known prevention of such deterioration.treatment with reagents such as formaldehyde has generally been practiced.

The couplers of the present invention do not require such a treatment. inherently having sufficient fastness. With respect, to stability against heat. experimental data for comparison are given in Example 2 hereinafter. The color photographic materials of the present inv'ention do not require any chemical treatment, lor example, with formaldehyde. for the improvement of the heat durability of images formed, and consequently, the development treatment can be simplified as a whole, which is one of the advantages of the present invention.

There are various methods for adding the couplers of the present invention to photographic emulsions. and some representative examples will be described below. a. A coupler is dissolved in an organic solvent which is dillicultly soluble in water and which has a high boiling point (of 200C or more, for example, up to a boiling point of 250C/l mmHg), and the resulting coupler solution is emulsified and dispersed in an aqueous medium and then added to a photographic emulsion. Organic solvents which are suitable for this method are,

for example, carboxylic acid esters such as the alkyl or I aryl esters of phthalic acid or citric acid, e.g., dibutyl phthalate, phosphoric acid esters such as the alkyl or aryl esters of phosphoric acid,e.g., tricresyl phosphate, amides such as alkyl or aryl amides of carboxylic acid, e.g., N,N-diethyl caproic acid amide, ethers such as the alky-lor aryl phenyl .ethers,'a1ky1 or aryl phenols, c.g., p-n-nonylpheno1,- 2-methy1-4-n-octy1pheno1, glycerin esters such as glycerides, etc. These classes and examples are merely cxemplary of suitable solvents having a high boiling point, the important functional characteristic.

b. A coupler is dissolved in a solvent which is relatively difficultly soluble'in water and which has a low boiling point, c.g., about 35 to 160C, preferably 60 to 130C. and the resulting'coupler solution is emulsitied and dispersed in an aqueous medium and then added to a photographic emulsion. The organic solvent used is removed during the preparation of photographic materials. Representative of solvents which are suitable for this methodare ethyl acetate, cyclohexanone. beta-butylethoxyethyl acetate, etc.

c. A coupler is dissolved in an organic solvent which is easily miscible with water and the resulting coupler solution is added to a photographic emulsion, whereby the coupler is dispersed therein in the formof fine colloidal particles. The solvent used can be removedduring the preparation of photographic materials or can be retained in'the emulsion layer. Solvents easily'miscible with water which are suitable for this method are, for example, dimethylformamidc, dimethylsulfoxide, N-' methylpyrrolidone ,glycerin, tet rahydrofuran, etc.

Suitable solvents for methods.(a) to (c) are disclosed in U.S. Pat, Nos..2,322,027; 2,835,579; 3,253,921; and 3,574,627. i

Depending upon (c) can be used optionally in the form of a mixture the solubility of the couplers -the solvents of the abovedescribed methods (a), (b), and

thereof. whereby the dispersion condition 01 the cou plers can be iinp roved.

ln additioi iia coupler can also be added according to another method which is similar to a water solution system, where a solvent as used in the above method (c) is mixed with wa ter anda base such as sodium hydroxide is further added thereto to form a mixed solvent. The coupler is'dissolved in the resulting mixed solvent to form an aqueous solution, and the resulting coupler aqueous solution is mixed with a photographic emulsionf For this addition method, couplers having a water-soluble group 'such as a carboxyl group in any of the residues R, R R- X, Y and Z of the above formula (1) are particularly suitable.

For preparing silver halide color photographic materials using couplers of the present invention, the couplers ofthepresentinvention represented by the above formula (1) can be used singly or in the form 01' a mix- .ture of the couplers, or moreover, the couplers of the present invention can also be used together with magcnta couplers other than those of the formula (1), for example, the magenta color couplers disclosed in U.S. Pat. Nos. 2,600,788; 2,725,292; 2,908,573; 2,983,608; 3,062,653; 3,311,476; 3,419,391; 3,468,666; 3,519,429; 3,558,319; and 3,582,322.1n addition, they can be used together with other water solution system magenta couplers in the same emulsion. Furthermore, a magenta coupler of the present invention represented by the formula (I) can be used together with other cyan or yellow couplers in the same emulsion layer, for the purpose of improving the color reproductivity of color photographic materials, as described in Japanese P atent Publn. No. 391/65.

A photographic emulsion containing one or more couplers of the present invention is applied on a conventional photographic support such as a film base or .baryta paper, and consequently, various color photopapers, etcQcan be prepared.

1n the above described phtog raphic emulsions, silver halides such as silver chloride, silver bromide, silver iodide, silver bromoiodide, silver iodochloride, silver iodobromochlori'de, ctc., can be used, the so-called converted halide silver halide grains as described in 1 Pat. No. 3,622,318 andBritish Patent 635,841 can i be used, and these photographic emulsions can optionally contain natural sensitizers present in gelatin, noble metal salts as well as reduction sensitizers, as disclosed in U.S. Pat, Nos. 1,574,944; 2,399,083; 2,410,689; 2,487,850; 2,521,925; 2,540,085; 2,642,361 and 2,983,609,411 addition, these emulsions can further contain optical scnsitiyers for imparting thereto appropriate color sensitivity as disclosed, for example, in U.S. Pat. Nosl 2,519,001;]2,666,761; 2,739,964; and

I 3,481,742, and can also contain conventional photographic additives 'such as antifogging agents, stabilizers, anti-staining agents, anti-irradiation dyes, gelatin plasticizers, gelatin hardeners,'coating auxiliaries, poly- I mers, etc. Suitable anti-fog'gants or stabilizers which 2,360,290; 2,403,721;1,704,713; 2,732,300; and

2,735,765; and suitable anti-irradiation dyes in U.S.

, Pat No. 3,605,546; suitable gelatin plasticizers in U.S.

Pat, Nos. 2.286,2l; 2,327,808; 2,322,085; 2,768,154;

2,808,331: 2.904.434; and 2,940,854; suitable gelatin hardeners in U.S. Pat. Nos. 3,232,763 4; 3,288,775; 3.635.718: 2,732,316: 3,017,280; 2,725,294 5; 2,983,611; 3,103,437; 2,586,168; 3,543,292; 3,321,313; 3,186,848; 3,490,91 l; and 3,671,256; suitable coating auxiliaries in U.S. Pat Nos. 3,415,649; 2,992,108: 3,068,101; 3,133,816; 2,831,766; and 3,666,478: suitable polymer materials in U.S. Pat. Nos, 2,290,289; 2,772,163; 2,852,382; and 3,619,195.

The color photographic materials of the present invention advantageously contain a p-substituted phenol derivative together with a 3-anilino-2-pyrazol-5-one compound of the formula (1), for increasing the stability of color photographs, Representative examples of psubstitutcd phenol derivatives which are particularly suitable for the color photographic materials of the present invention are, for example, the hydroquinone derivatives as described in U.S. Pat, Nos. 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, 2,710,801, and 2,816,028; the gallic acid derivatives as described in U.S. Pat, Nos. 3,457,079 and 3,069,262 and Japanese Patent Publn. No. 13496/68; the p-alkoxyphenols as described in U.S. Pat, Nos. 2,735,765 and 3,698,909; the p-oxyphenol derivatives as described in U.S. Pat. Nos. 3,432,300, 3,573,050 and 3,574,627 and U.S. Pat, application Ser. No. 213,540, filed Dec, 29, 1971,

These compounds are non-coupling compounds of the formula AOh wherein A is a substituted phenyl radical, including a phenyl having a fused heterocyclic group in the 4-5 position relative to the OH group. More specifically, A is defined as the residue of a hydroxy phenyl ether; a 6-hydroxy chroman; a 5-hydroxy coumaran; a hexahydro dibenzo furan-5-ol; and a 6,6- dihydroxy spirochroman.

Examples of such compounds are 1, 2,2-dimethyl-4-methyl-6-hydroxy-7octylchroman 2. 2,2-dimethyl-4-isopropyl-6-hydroxy-7-oetylchroman 3, 2'methy|-2-(4,8-dirnethyl)nonyl-6-hydroxy-7-(or- 8- )-octy1-chroman 4, 2-(N-methyl-N-phenyl)amino-3,3-dimethyl-5- hydroxycoumaran 5. 2-methyl-2-hexadecyl-6-hydroxy-7-t-butylchroman 6. 2,2-dimethyl-4-isopropyl-5-methyl-6-hydroxy-7 methyloxy chroman 7. 2,2,4,5-tetramcthyl-6-hydroxy-7.8-dimethoxychroman 8. 2'methyl2-hexadecyl-6-hydroxy-8-t-butyl chroman 9 2-methyl-2-( 4,8-dimethyl )nonyl-5 -methyl-6" hydroxy-7,8-dimethoxy chroman 2,2'-spirochroman 17. 2-hydroxy 3-octyl-5a-methyl-8-isopropyl- 5a,6,7,8,9,9a-hexahydrodibenzofuran l8 2-1N-methyl-N-tp-carboxy methyl )benzyl lamino-3,3-dimethyl-5-hydroxy-6-t-octyl coumaran 19. 2-hydroxy*5a-(N-methyl-N-phenyl) amino-521,6,7.8.9.9a-hexahydro dibenzofuran 20. 2-methyl-2-(4-methyl)-3-pcntenyl-6-hydroxy-7- t-octyl chroman 21. 2,2,5,7,8-pentamethyl-4-isopropyl-6-ehroman 22. aTocopherol 23, BTocopherol 24. y-Tocopherol 25, S-Tocopherol 26. 6.6-dihydroxy-4,4,4,4,7,7'-hexamethyl-bis- 27, 6.6'-dihydroxy-7,7'-di-t-butyl-4,4,4,4- tetramethylbis-2,2-spirochroman 28. 6,6'-dihydroxy-7,7'-dimethoxy-4,4,4,4- tetramethylbis-2,2spirochroman The hydrophilic colloid layers containing the 3- anilino2-pyrazol-5-one couplers of the present invention, in particular, gelatin layers, can be hardened with various kinds of crosslinking agents, as disclosed in U.S. Pat. Nos. 1,574,944; 2.399,083; 2,410,689; 2,487,850; 2,521,925; 2,540,085; 2,642,361; and 2,983,609. For example, inorganic compounds such as chromic acid and zirconium salts and aldehyde type cross-linking agents such as mucocliloric acid and 2- phenoxy'3-chloromalealdehyde acid as described in Japanese Patent Publn. No, 1872/71 can be used effectively in the present invention in many cases; and in particular, non-aldehyde type crosslinking agents such as polyepoxy compounds, as described in Japanese Patent Publn. No. 7133/59, po1y-( l-aziridinyl) compounds, as described in Japanese Patent Publn. No, 8790/62, and active halogen compounds, as described in U.S. Pat. Nos, 3,362,827 and 3,325,287, are especially useful in the actual practice of the present inven' tion.

Photographic materials containing couplers of the present invention'are treated according to conventional methods. More precisely, these materials after exposure thereof, are developed with a developer containing a p-phenylenediamine type developing agent. and then are bleach-fixed to form color images having excellent spectroabsorption characteristics and transpareney. Representative examples of developing agents suitable for development ofthe color photographic materials of the present invention are, for example, 4-(N,N-diethyl)aminoaniline, 4- N-ethyl-N-(Z- methanesulfonamidoethyl)amino -2-methylaniline, 4- N-ethyl-N-( heta-hydroxyethyl )amino-2-methylaniline, 4-(N,N-diethyl)amino-2-methy1aniline, etc,, as disclosed in J.Am, Chem, 800., vol 73, pages 3100 3125 (1951), 1. Plan, Sci, Eng, vol 8, No. 3, pages 137 (1964), C. E. K. Mees and T. H. James, The Theory of the Photographic Process, lllrd Ed., pages 294 295 (1966), and U.S. Pat. Nos. 2,592,364; 2,193,015.

Now, some preferred embodiments of the present invention will be exemplified in the following Examples, which, however, do not whatsoever limit the scope of the present invention. Unless otherwise indicated, all parts and percents are by weight.

EXAMPLE 1 A solution obtained by heating and dissolving 5g of the above described Coupler (22) of the present invention, 4ml of tricresyl phosphate and 15ml of ethylacetate at 60C was added to 50ml of an aqueous solution (60C) containing 5g of gelatin and 0.15g of sodium dodecyl-benzene sulfonate, and the solution mixture was stirred with a homogenizer to form a coupler dispersion. This coupler dispersion was mixed with 100g ofa photographic emulsion containing 5.6 X 10 mole of silver bromochloride (silver chloride; 55mol /r) and 10g of gelatin, and then, 5ml of a 3% acetone solution of triethylene phosphamide was further added thereto as a hardener, and finally, after the PH of the resulting mixture was adjusted to 6.5, this was applied on a cellulose t riacetate film base and then dried (thickness of dried film: 3.4 The thus manufactured photographic film was exposed in a conventional manner and then subjected to the following treatments, whereby a sharp magenta color image having a maximum absorption of 542 mu was obtained.

Treatment Steps:

1. Color Development 21C 14 minutes 2. Water Washing 30 seconds 3. First Fixation 4 minutes 4. Water Washing 4 minutes 5. Bleaching 8 minutes 6. Water Washing 4 minutes 7. Second Fixing 4 minutes 8. Water Washing 6 minutes Color Developer:

4-(N,N-Diethyl)amino'2- 2.5g methylaniline Hydrochloride Sodium Sulfite (anhydride) 10 g Sodium Carbonate (H 47 g Potassium Bromide 2g Water to make l liter (pH: 10.5) Fixing Solution:

Sodium Thiosulfate (6H O) 80g Sodium Sulfite (anhydride) 5g Borax 6g Glacial Acetic Acid 4ml Potassium Alum 7g Water to make 1 liter (pH: 4.5) Bleaching Bath:

Potassium Ferricyanide 100g Potassium Bromide 5g Boric Acid 10g Borax 5g Water to make 1 liter (pH: 7.2)

EXAMPLE 2 A solution obtained by heating and dissolving 5.0g of the above described Coupler (7) of the present'invention, 0.4g of 2.S-di-tert-octylhydroquinone, 7.0ml of tricresyl phosphate and 14ml of ethyl acetate at 60C was added to 50ml of an aqueous solution (60C) containing 5g of gelatin and O. 10g of sodium dodecylbenzene sulfonate, and the resulting solution mixture was stirred with a homogenizer to form a coupler dispersion. This coupler dispersion was mixed with 100g of a photographic emulsion containing 4.7 X 10 mole of silver bromochloride (silver chloride: 50 molVr) and 9g of gelatin, and then, 5ml of a 3% acetone solution of tricthylene phosphamide was further added thereto as a hardener, and finally, after the pH of the resulting mixture was adjusted to 7.0, this was applied on a resin coated paper and then dried (thickness of dried film: 2.9 t).

According to the same method as described above, other color photographic papers were prepared using the above described Couplers (l), (3) and (6) of the present invention and the above described known Couplers (A) and (B).

Step-exposure was imparted to each of the thus pre- Treatment Steps:

1. Color Development 30C 4 minutes 2. Bleach-fixation 2 minutes 3. Water Washing 2 minutes 4. Stabilization 2 minutes Color Developer:

Sodium Metahorate 25g Sodium Sulfite 2g Hydroxylamine (sulfate) 3g Potassium Bromide 0.5g 6-Nitrohenzimidazole (nitrate) 0.02g Sodium Hydroxide 4g Benzyl Alcohol 15.8ml Diethyleneglycol 20ml 4-{N-EthylN-( 2-methanesulfonamidoethyl 8g amino-Z-methylaniline-sesquisulfate Water to make 1 liter Bleach-fixing Solution:

Ferric Ethylenediamine Tetraacctate 45g Ammonium Thiocyanate 10g Sodium Sulfite 10g Ammonium Thiosulfate (607: ml Tetraspodium Ethylenediamine- 5g tetraacetate Water to make 1 liter Stabilization Bath (a):

Tartaric Acid 10g Lead Sulfate 10g Sodium Metaborate 20g Water to make 1 liter Stabilization Bath (b):

Tartaric Acid 10g Lead Sulfate 10g Sodium Metahorate 20g Formalin (4071) 10ml Water to make 1 liter Each specimen was exposed for 4 hours at C, for 2 weeks at 60C, 75% RH and for 2 weeks to the light from a fluorescent lamp, and the degree of density reduction per the initial density of the magenta color image formed was measured in each case. The results obtained are shown in the following Table 4.

TABLE 4 FASTNESS OF COLOR IMAGES TO HEAT AND LIGHT (degree of density reduction ('74 per initial density) Coupler Sta- 120C. 4Hours 60C,75'/1RH Fluorescent bil- Initial 2 Weeks Lamp iz- Density initial 2 Weeks ing 0.5 1.0 Density Initial Bath 0.5 1.0 Density invention (a) 7 5 5 4 21 Coupler (7) lnvention (a) 8 7 2 0 18 Coupler (l lnvention (a) 7 6 6 4 l9 Coupler (3) lnvention (a) 6 4 5 3 20 Coupler (6) Known (a) 10 7 9 7 23 Coupler (A) Known (a) 67 40 33 19 25 Coupler (B) Known (b) 8 3 9 6 23 Coupler (B) As is apparent from the results contained in Table 4 above, the couplers of the present invention yield color images having a fastness to heat which is equal to or higher than that of the known Coupler (A), and further they do not require any stabilization bath containing formalin, unlike the other known Coupler (B), and impart extremely fast color images. in addition, it can be seen that color images obtained from the present couplers have sufficient fastness to light.

EXAMPLE 3 Several kinds of solutions were prepared by heating (at 60C) and dissolving (a) 5.2g of the above described Coupler (6) of the present invention and (b) 104ml, 7.28m], 4.16mi, 2.6m], 1.04ml and Oml of tricresyl phosphate (TCP) and (c) 10ml, 14ml, 17ml,

il9ml, 21ml, and 22ml of ethyl acetate, respectively.

tion of triethylene phosphamide was added thereto as a hardener, and finally, after the pH of the resulting mixture was adjusted to 7.0, this was applied on a cellulose triacetate film base and then dried. in exactly the same way, a plurality of coupler dispersions was prepared by using (a) 4.4g of the above described known Coupler (B) and (b) 8.8ml, 6.16ml, 3.52mi, 2.2ml, 0.88m] and Oml of tricresyl phosphate and (e) 9ml, 12ml, 14ml, 16ml, 17ml and 18ml of ethyl acetate, respectively, and each of the resulting coupler dispersions was mixed with [g of the above described photographic emulsion and then coated and dried. Each of the resulting photographic films thus prepared was treated with the following developer for 12 minutes at 21C, and then the same treatments, fixation, bleaching and fixation, as described in Example I were performed consequently to obtain magenta color images. The main absorption wavelength peak of the resulting magenta color images was as shown in the following Table 5.

ethyl}amimrlmethylaniline sesquisulfate TABLE Ratio of Trieresyl Phosphate (mll/Coupler (g) and Main Absorption Wavelength Peak (mu) Ratio of invention Known TCP/(oupler Coupler (6) Coupler (B) TABLE 5-Continuecl Ratio of Tricresyl Phosphate (mil/Coupler (g) and Main Absorption Wavelength Peak tmp.)

It can be seen from the results contained in Table 5 above that the Coupler (6) of the present invention yields good color images of excellent transparency even through the amount of the non-volatile solvent of high boiling point used is decreased, and further. the Coupler (6) did not separate out in the dispersion as well as in the coated film. As is apparent from the results in this Table, a decrease in the amount of nonvolatile solvents of high boiling points used for the couplers of the present invention scarcely causes any variation in the spectroabsorption characteristics of the resulting color images, and therefore, it is possible to decrease the amount of the solvents for the couplers of the present invention with the result that the thickness of the coated films can be decreased.

EXAMPLE 4 On a polyethylene coated paper was applied a bluesensitive silver bromochloride emulsion containing alpha-pivaloyl-alpha-(5,5-dimethyl-3-hydantoinyl)-2- chloro-5-[alpha-(2,4-di-tert-pentylphenoxy)- butylamido1-acetoanilide to form a first layer having a thickness of 3.0 11., and then gelatin was applied thereupon to form a second layer of a thickness of 1.5 ,u.

A solution obtained by heating (60C) and dissolving 5.0g of the above described Coupler (7) of the present invention, 0.5g of 2,S-di-tert-octylhydroquinone, 0.5g of 6,6-dihydroxy-7,7'-dimethoxy-4,4,4',4'- tetramethyl-bis-2,2-spiroehroman, 5.0m] of tricresyl phosphate and 20ml of ethyl acetate was added to 50ml of an aqueous solution (60C containing 5g of gelatin and 0.16g of sodium dodecylbenzenesulfonate, and then the resulting mixed solution was stirred with a homogenizer to form a coupler dispersion. This coupler dispersion was mixed with g of a green-sensitive photographic emulsion containing 4.7 X 10' mole of silver bromochloride (silver chloride: 50 mol%) and 9g of gelatin, and then 5ml of a 3% acetone solution of triethylene phosphamide was added thereto as a hardener, and finally, after the pH of the resulting mixture was adjusted to 7.0, this was applied on the above coated material to form a third layer of a thickness of 3.5 ;1.. Next, gelatin containing 2-( 5 chlorobenzotriazol-Z-yl)-4-methyl-6tert-butylphenol and 2-(benzotriazol-2-yl)-4-tert-butylphenol was further applied thereupon to form a fourth layer of a thickness of 1.5 u, and on this fourth layer was applied further a red-sensitive emulsion containing 2-[alpha- (2,4-di-tert-pentylphenoxy)butylamido]-4,6 -dichloro- S-methyl-phenol to form a fifth layer of a thickness of 2.5 ,u. and then gelatin was superposed thereon to form an uppermost layer of a thickness of l .1., whereby a color print paper was prepared (Sample a).

In place of the above Coupler (7) were used 4.0g of a known coupler 1-(2,4,6-trichlorophenyl)-3- 3-[2- (2,4-di-tert-pentylphenoxy )butylamido]benzamide-2- pyrazol-S-one, as a magenta coupler, and otherwise the same procedures used in the preparation of Sample a were carried out to form another color print paper (Sample b).

To these samples was imparted sensitometric exposure to green light, and development and bleachfixation were carried out according to the procedure described in Example 2, and finally, stabilization treatment was performed with Stabilizer Bath (a) hereinbefore described. Sample a yielded a magenta color image having a maximum absorption at 543 me and the Sample [2 yielded a magenta color image having a maximum absorption at 550 mu. These color prints were left in air where the relative humidity was adjusted to 75% at 60C, for 4 weeks, whereby the magenta color image obtained from the color photographic material of the present invention (Sample a) deterioratedonly to an extent of at an initial density of 1.0, while the color image obtained from the photographic material containing the known coupler (Sample b) deteriorated to an extent of 17%. a

These samples were exposed through a transparency having color negative images and then subjected to development treatment according to the above described procedures to obtain color prints. The redpart of the print obtained from the Sample a of the present invention was sharp and less dark, as compared with that obtained from the Sample b containing the known coupler. This isbecause of the characteristic, as described above, that the spectroabsorption curve of the magenta color image obtained from a coupler of the present in vention is sharply cut at the longer wavelength side, as compared with any other known coupler.

EXAMPLE 5 On a cellulose triacetate film base were coated a first layer of a red-sensitive: silver vbromoiodide emulsion containing l-hydroxy-2-tetradecyl naphthamide (thickness: 5p.) and a second layer of gelatin containing 2,5-di-tert-octylhydroquinone (thickness: l.0 a).

A solution obtained by heating ,(60C)-and dissolving 14.6g of the above described Coupler (22) of the-present invention, 2.0g of the above described Coupler (14) of the present invention, 8ml of-tricresyl phosphate and 50ml of ethyl acetate was added to l50ml of an aqueous solution (60C) containing g of gelatin and 0.4g of sodium dodecylbenzene sulfonate, and the resulting mixture solution was stirred witha homogenizer to form a coupler dispersion, This coupler disper- 2,5-di-tert-octylhydroquinone (thickness: 1.5 a), and v further a fifth layer of a blue-sensitive silver bromoiodide emulsion containing alpha-(p-methoxybenzoyl)- alpha-(N-phthalimido)-2-chloro5-[ganima (2,4-ditert-pentylphenoxy) butylamido]acetoanilide' (thickness: 5.0 a), and finally a protective'la yer of gelatin (thickness: 1.0 ,u.) as an uppermost layer. 'a jcolor negative photographic material was prepar edl This film was developedflifter exposure, according to the following treatment steps. whereby an excellent color negative was obtained having high sensitivity. good gradation and excellent image quality. In addition, it was shown-that the blue light density thereof .was almost constant*regardless of the degree of green light exposure and that a' proper color correction was completed.

Treatment Steps:

lv Color Development 38C 3 minutes *2. Stopping i Y lminute 3, WaterWashing l minute 4. Bleaching 2 minutes 5, Water Washing 1 minute 6. Fixation 2 minutes '7, Water Washing l minute 8. Stabilization l minute Color Developer: i

, Sodium Hydroxide 2g Sodium Sulfite 2g Potassium Bromide 0.4g Sodium Chloride lg Borax 4g Hydroxylamine Sulfate 2g Ethylenediaminc Tetraacetic Acid 2g 7 4-{N-ethyl-N -t2-hydroxyethyl)amino}-2- 4g methylaniline sesquisulfate Water to make l liter Stopping Solution? Sodium Thiosullate 10g Ammonium Thiosulfate('70'/() 30ml Sodium Acetate 5g Acetic Acid 20ml Potassium Alum l5g 'Water to make 1 liter Bleaching Solution: j

Ethylenediamine Tetraacetate 100g (iron ("U-sodium salt-2H O I Potassium Bromide g Ammonium Nitrate 50g Borie Acid 5g Aqueous Ammonia to adjust the pH to 5.0

" Water to make l liter Fixing Solution:

Sodium Thiosullate 150g Sodium Sulfite g Borax I 12g Glacial Acetic Acid l5ml Potassium Alum 20g 1 Water to make l liter- Stabilization Bath:

Boric Acid 5g Sodium Citrate 7 5g Sodium Metaborate (4H O) 3g Potassium Alum 15g Water to make 1 liter EXAMPLE 6 A solution obtained by heating (at 60C) and disi solving 5g of each of the invention Couplers (1), (2),

( (18), (20), (21), (22), (24), (25), (26) and (27) and 8ml of tricresyl phosphate and 10ml of ethyl acetate was dispersed, mixed with a photographic solution, coated and dried, and then developed, in a manner similar to Example I, to form a sharp image having the following maximum absorption (my).

-Continued Maxi Maxi Maximum mum mum Ahsorp- Ahsorp- Absorp- Coupler tion Coupler tion Coupler lion (3! 546 546 (23) 54l (4] 546 (lb) 539 (24) 541 (6) 546 (I7) 53) (15) 536 47) 540 (I8) 539 (26) 542 (X) 546 534 (27) 536 While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to. one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What is claimed is: i

1. A silver halide photographic emulsion containing at least one 3-anilino-2-pyrazol-5-one type nondiffusing magenta coupler of the following formula (I):

wherein said sulfamoyl group is in the metaor paraposition, R represents an aryl group or a heterocyclic group selected from the group consisting of a 2- thiazolyl, a Z-benzothiazolyl, a 2-benzoxazoly, a 2- oxazolyl, a 2-imidazolyl or a 2benzimidazolyl group; R, and R cach represents a hydrogen atom or an alkyl group, an aryl group, or a heterocyclic group selected from the group consisting of a benzimidazolyl group or a benzothiazolyl group or a group of non-metallic atoms necessary for forming a heterocyclic group together with the N-atom of the sulfamoyl group selected from the group consisting of a morpholine or piperidine ring; X and Y each represents an alkyl group, an aryl group, alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an amido group, a hydroxy group, a cyano group, a nitro group or a halogen atom and Y additionally represents a hydrogen atom; and Z represents a hydrogen atom or a coupling removable residue which can be removed by :coupling with an oxidation product of a primary aromatic amino developing agent.

2. The silver halide photographic emulsion of claim 1, wherein R represents a phenyl group substituted, in at least one ortho-position thereof, by an alkyl group, an alkoxy group, an alkylthio group, a cyano group or a halogen atom; R, and R each represents a hydrogen atom or an alkyl group or an alkyl group substituted with an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an acylamino group "or a carbamoyl group, with both R, and R not being simultaneously hydrogen atom and with the total numher of carbon atoms included in both R, and R ranging from 8 to 32; X represents a halogen atom, or an alkoxy group having 5 or less carbon atoms or an aryloxy group having 12 or less carbon atoms; and Y represents hydrogen atom. g I

3. The silverhalidephotographic emulsion of claim 1, wherein Z represents ahydrogen atom, a halogen 5 atom, a thiocyano group,'an acyloxy group, an aryloxy group, an arylazo group, a heteroazo group, an arylthio group or a heterothio group.

4. The silver halide photographic emulsion of claim 1, wherein X represents a methoxy group, an cthoxy group, a propoxy group, a'fluorine atom, a chlorine atom, a bromine atom or a phenoxy group.

5. The silver halide photographic emulsion of claim 1, wherein the R R NSO- -moiety is in the 4-position of the anilino group.

6. The silver halide photographic emulsion of claim 1, wherein the R R NSO- -moiety is in the 5-position of the anilino group.

7. The silver halide photographic emulsion of claim 1, wherein R has the following formula:

in which U, represents a halogen atom, or an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or a cyano group; U represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or a cyano group; and U U and U each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cyano group, an acylamino group, a carbamyl group, an ureido group, a sulfonamido group, a sulfamyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkoxycarbonyl group, a carboxy group or an arylcarbonyl group.

8. The silver halide photographic emulsion of claim 1, wherein said non-diffusing magenta coupler is;

l-(2,4,6-trichlorophenyl)-3-(2-chloro-4- tetradecylsulfamoylanilino)-2-pyrazol-5-one,

l-( 2,4,6-trichlorophenyl )-3-(2-chloro-5- tetradecylsulfamoylanilino)-2-pyrazol-5-one,

l-(2,4,6-trichlorophenyl)-3-{2-chloro-5-[3-(2,4di-

'tert-pentylphenoxy )propylsulfamoyllanilino) -2- pyrazol-S-one,

l-( 2,4,6-trichlorophenyl )-3-{ 2-chloro-5-[3-( 3- pentadecylphenoxy) propylsulfamoyl]anilino}-2- pyrazol-S-one,

l-( 2,4,6-trichlorophenyl )-3- {2-chloro-4-[2-( 3-tertbutyl-4-hydroxyphenoxy)tetradecylsulfamoyllanilino }2-pyrazole-5-one, or

l-( 2,6-dichloro-4-methoxyphenyl )-3-{2-chloro-5-[ 3- (2,4-di-tert-pentylphenoxy)propylsulfamoyl- ]anilino} 2-pyrazol-5-one.

9. A silver halide photographic element comprising a support and having thereon at least one silver halide photographic emulsion layer of claim 1.

10. The silver halide photographic element of claim 1, wherein R represents a phenyl group substituted, in

at least one .ortho-position thereof, by an alkyl group, an alkoxy group, an alkylthio group, a cyano group or a halogen atom; R and R each represehts a hydrogen atom or an alkyl group.- or an alkyl group substituted with'an alkoxy group,.an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an acylamino group or a carbamoyl group, with both R and R not being simultaneously a hydrogen atom and with the total number of carbon atoms included in both R and R ranging from 8 to 32; X represents a halogen atom, an alkoxy group having or less carbon atoms or an aryloxy group having 12 or less carbon atoms; and Y represents a hydrogen atom.

11. The silver halide photographic element of claim 1, wherein Z represents a hydrogen atom, a halogen atom, a thiocyano group, an acyloxy group, an aryloxy group, an arylazo group, a heteroazo group, an arylthio group or a heterothio group.

12. The silver halide photographic element of in claim 1, wherein X represents a methoxy group, an ethoxy group, a propoxy group, a fluorine atom, a chlorine atom, a bromine atom or a phenoxy group.

13. The silver halide photographic element of claim 1, wherein the R R NSO -moiety is in the 4-position of the anilino group.

14. The silver halide photographic element of claim 1, wherein the R R NSO -moiety is in the 5-position of the anilino group.

15. The silver halide photographic element of claim 1, wherein R has the following formula:

group, an aryloxy group, an arylthio group or a cyano cyano group; and U U and U each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cyano group, an acylamino group, a carbamyl group, an ureido group, a sulfonamido group, a sulfamyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkoxycarbonyl group, a carboxy group or an arylcarbonyl group.

16. The silver halide photographic element of claim 1, wherein said non-diffusing magenta coupler is;

l-(2,4,6-trichlorophenyl)-3-(2-chloro-4- tetradecylsulfamoylanilino)-2-pyrazol-5-one,

l-(2,4,6-trichlorophenyl)-3-(2-chloro-5- tetradecylsulfamoylanilino)-2-pyrazol-5-one,

l-( 2,4,6-trichlorophenyl)-3- {2-chloro-5-[3-(2,4,-ditert-pentylphenoxy )propylsulfamoyl anilino} -2- pyrazol-S-one,

l-( 2,4,6-trichlorophenyl )-3-{2-chloro 5-[3 3- pentadecylphenoxy) propylsulfamoyl]anilino}-2- pyrazol-S-one,

l-(2,4,6-trichlorophenyl )-3- {2-chloro-4-[2-( 3-tertbutyl-4-hydroxyphenoxy)tetradecylsulfamoyl- ]anilino}-2-pyrazole-5-one, or

l-(2,6-dichloro-4-methoxyphenyl)-3-{2-chloro-5-[3- (2,4-di-tertpentylphenoxy)propylsulfamoyl- ]anilino}2-pyrazol-5-one.

17. The silver halide photographic emulsion of claim 1, wherein R represents a phenyl group substituted, in at least one ortho-position thereof, with an alkyl group, an alkoxy group, an alkylthio group, a cyano group or a halogen atom; R and R each represents a hydrogen atom or an alkyl group or an alkyl group substituted with an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an acylamino group or a carbamoyl group, with both R, and R not being simultaneously hydrogen atoms and with the total number of carbon atoms included in both R and R ranging group; U represents a hydrogen atom, a halogen atom,

an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or a from 8 to 32; X represents a halogen atom, or an alkoxy group having 5 or less carbon atoms or an aryloxy group having 12 or less carbon atoms; Y represents a hydrogen atom; and Z represents a hydrogen atom or .a coupling removable residue which can be removed by coupling with an oxidation product of a primary aromatic amino developing agent. 

1. A SILVER HALIDE PHOTOGRAPHIC EMULSION CONTAINING AT LEAST ONE 3-ANILINO-2-PYRAZOL-5-ONE TYPE NONDIFFUSING MAGENTA COUPLER OF THE FOLLOWING FORMULA (I):
 2. The silver halide photographic emulsion of claim 1, wherein R represents a phenyl group substituted, in at least one ortho-position thereof, by an alkyl group, an alkoxy group, an alkylthio group, a cyano group or a halogen atom; R1 and R2 each represents a hydrogen atom or an alkyl group or an alkyl group substituted with an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an acylamino group or a carbamoyl group, with both R1 and R2 not being simultaneously hydrogen atom and with the total number of carbon atoms included in both R1 and R2 ranging from 8 to 32; X represents a halogen atom, or an alkoxy group having 5 or less carbon atoms or an aryloxy group having 12 or less carbon atoms; and Y represents hydrogen atom.
 3. The silver halide photographic emulsion of claim 1, wherein Z represents a hydrogen atom, a halogen atom, a thiocyano group, an acyloxy group, an aryloxy group, an arylazo group, a heteroazo group, an arylthio group or a heterothio group.
 4. The silver halide photographic emulsion of claim 1, wherein X represents a methoxy group, an ethoxy group, a propoxy group, a fluorine atom, a chlorine atom, a bromine atom or a phenoxy group.
 5. The silver halide photographic emulsion of claim 1, wherein the R1R2NSO2-moiety is in the 4-position of the anilino group.
 6. The silver halide photographic emulsion of claim 1, wherein the R1R2NSO2-moiety is in the 5-position of the anilino group.
 7. The silver halide photographic emulsion of claim 1, wherein R has the following formula:
 8. The silver halide photographic emulsion of claim 1, wherein said non-diffusing magenta coupler is; 1-(2,4,6-trichlorophenyl)-3-(2-chloro-4-tetradecylsulfamoylanilino)-2 -pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradecylsulfamoylanilino)-2 -pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(3-(2,4-di-tert -pentylphenoxy)propylsulfamoyl)anilino)-2-pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(3-(3-pentadecylphenoxy) propylsulfamoyl)anilino)-2-pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-4-(2-(3-tert-butyl-4 -hydroxyphenoxy)tetradecylsulfamoyl)anilino)-2-pyrazole-5-one, or 1-(2,6-dichloro-4-methoxyphenyl)-3-(2-chloro-5-(3-(2,4-di-tert -pentylphenoxy)propylsulfamoyl)anilino)-2-pyrazol-5-one.
 9. A silver halide photographic element comprising a support and having thereon at least one silver halide photographic emulsion layer of claim
 1. 10. The silver halide photographic element of claim 1, wherein R represents a phenyl group substituted, in at least one ortho-position thereof, by an alkyl group, an alkoxy group, an alkylthio group, a cyano group or a halogen atom; R1 and R2 each represents a hydrogen atom or an alkyl group or an alkyl group substituted with an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an acylamino group or a carbamoyl group, with both R1 and R2 not being simultaneously a hydrogen atom and with the total number of carbon atoms included in both R1 and R2 ranging from 8 to 32; X represents a halogen atom, an alkoxy group having 5 or less carbon atoms or an aryloxy group having 12 or less carbon atoms; and Y represents a hydrogen atom.
 11. The silver halide photographic element of claim 1, wherein Z represents a hydrogen atom, a halogen atom, a thiocyano group, an acyloxy group, an aryloxy group, an arylazo group, a heteroazo group, an arylthio group or a heterothio group.
 12. The silver halide photographic element of in claim 1, wherein X represents a methoxy group, an ethoxy group, a propoxy group, a fluorine atom, a chlorine atom, a bromine atom or a phenoxy group.
 13. The silver halide photographic element of claim 1, wherein the R1 R2NSO2-moiety is in the 4-position of the anilino group.
 14. The silver halide photographic element of claim 1, wherein the R1R2NSO2-moiety is in the 5-position of the anilino group.
 15. The silver halide photographic element of claim 1, wherein R has the following formula:
 16. The silver halide photographic element of claim 1, wherein said non-diffusing magenta coupler is; 1-(2,4,6-trichlorophenyl)-3-(2-chloro-4-tetradecylsulfamoylanilino)-2 -pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradecylsulfamoylanilino)-2 -pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(3-(2,4,-di-tert -pentylphenoxy)propylsulfamoyl)anilino)-2-pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(3-(3-pentadecylphenoxy) propylsulfamoyl)anilino)-2-pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-4-(2-(3-tert-butyl-4 -hydroxyphenoxy)tetradecylsulfamoyl)anilino)-2-pyrazole-5-one, or 1-(2,6-dichloro-4-methoxyphenyl)-3-(2-chloro-5-(3-(2,4-di-tert -pentylphenoxy)propylsulfamoyl)anilino)-2-pyrazol-5-one.
 17. The silver halide photographic emulsion of claim 1, wherein R represents a phenyl group substituted, in at least one ortho-position thereof, with an alkyl group, an alkoxy group, an alkylthio group, a cyano group or A halogen atom; R1 and R2 each represents a hydrogen atom or an alkyl group or an alkyl group substituted with an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an acylamino group or a carbamoyl group, with both R1 and R2 not being simultaneously hydrogen atoms and with the total number of carbon atoms included in both R1 and R2 ranging from 8 to 32; X represents a halogen atom, or an alkoxy group having 5 or less carbon atoms or an aryloxy group having 12 or less carbon atoms; Y represents a hydrogen atom; and Z represents a hydrogen atom or a coupling removable residue which can be removed by coupling with an oxidation product of a primary aromatic amino developing agent. 